Sulfonamide additives for sulfur vulcanizable polymers

ABSTRACT

Sulfonamides such as N,N&#39;&#39;-bis (morpholinothio)-N,N&#39;&#39;-ethylenebis(N-methyl-p-toluenesulfonamide) are used to affect the vulcanization characteristics of sulfur vulcanizable polymers by increasing the state of vulcanization and/or improving scorch resistance and/or increasing the rate of vulcanization.

United States Patent Hopper et al.

Aug. 5, 1975 SULFONAMIDE ADDITIVES FOR SULFUR VULCANIZABLE POLYMERS Inventors: Roger J. Hopper, Akron; John P.

Lawrence, Stow, both of Ohio Assignee: The Goodyear Tire & Rubber Company, Akron, Ohio Filed: May 23, 1974 Appl. No.: 472,765

Related US. Application Data Division of Ser. No. 266,009, June 26, 1972, Pat. No. 3,856,762.

US. Cl... 260/79.5 B; 260/79.5 A; 260/79.5 P; 260/780; 260/791; 260/792 Int. Cl. C08F 28/00 Field of Search 260/79.5 A, 79.5 P, 79.5 B, 260/780, 791, 792

' [56] References Cited UNITED STATES PATENTS 3,678,017 7/1972 Shelton et al. 260/79.5 B 3,703,500 ll/l972 Nast et al. 260/79.5 B

Primary Examiner--Ronald W. Griffin Attorney, Agent, or FirmF. W. Brunner; J. A. Rozmajzl 7 Claims, No Drawings SULFONAMIDE ADDITIVES FOR SULFUR VULCANIZABLE POLYMERS This application is a division of our application Ser. No. 266,009, filed June 26, 1972, now US. Pat. No. 3,856,762.

This invention relates to compounds which generally function to increase the state (degree) of vulcanization when used during the sulfur vulcanization of rubbers by donating sulfur to the system. This invention also relates to compounds which provide a vulcanizable polymer with balanced processing and vulcanization characteristics. In addition, it relates to compounds which retard vulcanization during the processing of vulcanizable rubbery compositions. It also relates to compounds which function as activators, that is, secondary accelerators in sulfur type vulcanization systems. It also relates to processes for increasing the state of vulcanization of sulfur vulcanizable rubbery compositions and either increasing scorch delay periods and/or increasing vulcanization rates. It also relates to the vulcanized products resulting therefrom.

The physical properties of a vulcanized composition are related to its state of vulcanization. Often, as the state of vulcanization is increased, certain physical properties are improved. Rubber additives such as sulfur donors can be used therefore to increase the state of vulcanization or to permit the use of lesser amounts of free sulfur.

Scorching during the processing of rubber is due to the premature or insipient vulcanization which can occur during any of the steps involved in the processing of the rubber prior to the final vulcanization step or during storage between said processing steps. Whereas a properly compounded unscorched rubber formulation can be die extruded or sheeted smoothly from a calender without lumping, a scorched material often becomes wavy or lumpy after sheeting and must be discarded. It is therefore desirable that rubber additives be used which reduce scorching. Such compounds are commonly referred to as retarders.

It is often desirable to increase the rate at which rubbery compositions are vulcanized. Sulfur vulcanizable rubbery compositions containing free sulfur are made to vulcanize more rapidly by the addition of an accelerator compound. Often the accelerator compound is referred to as a primary accelerator and is used in combination with another accelerator called an activator or secondary accelerator which further increases the vulcanization rate.

It is an object of this invention to provide sulfur donors which will increase the state of vulcanization of vulcanized rubbery polymers as well as compounds which are secondary accelerators (activators) and/or retarders (scorch inhibitors). Another object of the present invention is to provide processes which will improve the scorch resistance and rate of vulcanization of vulcanizable rubbery polymers and also the state of vulcanization of sulfur vulcanized rubbers.

The objects of the present invention are accomplished by a sulfur vulcanizable combination of a sulfur vulcanizable rubber and at least one compound containing the moiety said compound being selected from wherein A is an N,N disubstituted radical selected from the group consisting of v a. an N,N disubstituted radical which is a derivative of a heterocyclic diamine and wherein R and R can be joined through a CH group to constitute with the SO N group a heterocyclic ring radical, eg a sultam ring, wherein R and R are selected from the group consisting of alkyl radicals having 1 to 20 carbon atoms, cycloalkyl radicals having 5 to 20 carbon atoms, aralkyl radicals having 7 to 20 carbon atoms, and aryl radicals having 6 to 20 carbon atoms (e.g., phenyl, p-tolyl, nitroaryl, alkoxy aryl and haloaryl), and wherein R and R can be joined through a member of the group consisting of CH O, and -S- to constitute with the attached nitrogen atom a heterocyclic ring, and wherein R and R are selected from the group consisting of those radicals described for R and R (with the exception that neither R nor R can be an aryl radical) and may join to form the heterocyclic ring described for R and R and in addition either or both R and R can be hydrogen or cyanoalkyl radicals having 3 to 21 carbon atoms, wherein R is selected from the group consisting of alkylene radicals having 1 to 10 carbon atoms, cycloalkylene radicals having 6 to 20 carbon atoms and arylene radicals having 6 to 20 carbon atoms and wherein X is an alkylene radical containing 2 to 10 carbon atoms or a cycloalkylene radical containing to carbon atoms. Preferably R is methyl, ethyl, Z-propyl, nbutyl, n-propyl, phenyl, p-tolyl, p-chlorophenyl, dimethylamino, morpholino, piperidino, pmethoxyphenyl, p-nitrophenyl or cyclohexyl.

Preferably R is methyl, ethyl, 2-propyl, t-butyl, nbutyl, n-propyl, phenyl, p-tolyl, p-chlorophenyl, cyclohexyl, p-methoxyphenyl or p-nitrophenyl.

Preferably the radical is morpholino, 2,6-dimethylmorpholino, piperidino, diethylamino, diisopropylamino, 3- methylpiperidino, t-butyl amino, dicyclohexylamino, N-B-cyanoethylcyclohexylamino, N-B-cyanoethyl-tbutylamino, N-B-cyanoethyl-n-butylamino, N- ethylbenzylamino, dibenzylamino, N-cyanomethylcyclohexylamino, N-cyanomethyl-n-butylamino, bis-(B- cyanoethyl )amino, amino dimethylamino, N- methylethylamino, pyrrolidino or tert-octylamino.

Preferably R is ethylene, 1,3-propylene, 1,4-

cyclohexylene or p-phenylene.

Preferably when A is an N,N' disubstituted radical which is a derivative of a heterocyclic diamine, the diamine is piperazine, imidazolidine, hexahydropyrimidine or homopiperazine, said amines (radicals) being unsubstituted or substituted on the ring carbons by methyl groups, the total number of methyl groups being less than three. It should be understood that the above radicals need not actually be derived from the above diamines but need only be the radicals which can be derived from said diamines. That is, the compounds are not limited to their method of preparation.

More preferably A is piperazine, 2,5-dimethylpiperazine, imidazolidine, hexahydropyrimidine, homopiperazine, N,N'-dimethylethylenediamine, N,N-dimethyl- 1,3-propylenediamine, N,N-dimethyl-l ,6- hexamethylenediamine, N,N-dimethyl- 1 ,4- cyclohexylenediamine, 4,4-ethylenedi(piperidine), 4,- 4'-trimethylenedi(piperidine), 4,4-tetramethylenedi(- piperidine) or 4,4-hexamethylenedi(piperidine).

One preferred class of compounds used within the practice of the present invention are those containing a sultam' ring formed by the joining of R and R. Preferably the sultam ring contains 3 to 10 carbon atoms. The ring carbon atoms preferably are 3 to 6 in number, most preferably 3. Preferred radicals are those which can be derived from propanesultam, butanesultam, benzylsultam and 1,8-naphthosultam.

Compounds which act both as retarders and activators in butadiene/styrene elastomers (SBR) include compounds according to structural formula I where R is p-tolyl, p-chlorophenyl or dimethylamino, R ismethyl or p-tolyl or R and R are joined to form a propanesultam ring and 4 is morpholino, 2,6-dimethylmorpholino, piperidino, dicyclohexylamino, N-B-cyanoethylcyclohexylamino or N-B-cyanoethyl-t-butylamino. The compounds of structural formula II where R, R and is piperidino, 2,6-dimethylmorpholino, diisopropylamino, dicyclohexylamino or 3 methylpiperidino. The compounds of structural formula I" where R and R are as described above and A is the N,N disubstituted radical which is a derivative of 4,4-trimethylenedi(piperidine) are also both activators and retarders in natural rubber. Compounds where R, R and are as described above and in addition where R is ptolyl,

is morpholino, N-B-cyanoethylcyclohexylamino or N-,B-cyanoethyl-t-butylamino and A is a derivative of piperazine, are normally retarders in natural rubber. Also acting as retarders are any of the above, (and in addition, R may be ptolyl,

may be morpholino, N-,B-cyanoethylcyclohexylamino or N-B-cyanoethyl-t-butylamino, and A is a derivative of piperazine) are normally retarders. Also acting as retarders in natural rubber are compounds where R, R, and

. 7 When used with a conventional primary accelerator, the compounds of structural formulae (1), (11) and (III) provide a vulcanizable polymer with balanced processing and vulcanization characteristics. In many vulcanization systems they provide both improved scorch resistance and improved activation characteristics. In systems where they provide only improved scorch resistance or improved activation characteristics, they do so without adversely affecting the scorch resistance or conversely the activation characteristics. This is unique in that conventional retarders normally adversely affect vulcanization rates, much less improve the rate; while conventional activators normally adversely affect scorch, much less improve scorch resistance. Whether these compounds act as both activators and retarders, or just as an activator, or just as a retarder, is not only dependent upon the primary accelerator being used but also upon the particular polymer being vulcanized as well as the particular sulfur donor compound of the present invention being used. The effect of accelerator systems, polymeric environment and different sulfur donor compounds is illustrated herein. It should be noted, however, that regardless of the accelerator system used or the particular polymer vulcanized, the compounds almost always act as sulfur donors. In any case, the sulfonamides of the present invention will act at least as one of the following; a sulfur donor, an activator or a retarder.

The sulfonamides of the present invention can be prepared by reaction of an aminesulfenyl chloride with dithiobis(amine) [German Pat. No. 965,968 (1954)],

or by reaction of a secondary amine with sulfur dichloride in the presence of an organic acid acceptor [German Pat. No. 1,131,222 (1962)]. Generally a solution of the aminesulfenyl chloride in an inert solvent is added to a solution or suspension of the sulfonamide,

sulfamide, or sultam (or its alkali metal salt), also in an inert solvent.

Alternatively, the delayed action activators of the present invention can be prepared by reaction of a sulfonamide-, sulfamide-, or sultam-N-sulfenyl chloride with an appropriate amine in the presence of an organic acid acceptor such as triethylamine, pyridine, or

an excess of the amine which is entering into the reaction with the sulfenyl chloride. The sulfonamide-, sulfamide-, and sultam-N-sulfenyl chlorides, in turn, are readily prepared by any of the methods found in the literature such as by chlorination of an N,N-dithiobis(- sulfonamide), (sulfamide) or (sultam) [German Pat. No. 1,101,407 (1961)], or by reaction of an alkali metal salt of a sulfonamide, sulfamide, or sultam (or its acidic form in the presence of an organic acid acceptor) with sulfur dichloride [German Pat. No. 1,156,403 (1964)]. Generally, an amine is added to a solution of the sulfonamide, sulfamide-, or sultam-N-sulfenyl I chloride in an inert solvent. The performance of the 1 compounds of the present invention as retarders, activators or in increasing the state of vulcanization is not I dependent upon their method of preparation.

as carbon black, zinc oxide, antidegradants and stearic acid. They can be used in a sulfurless system with an accelerator (a sulfur donor or otherwise), preferably a primary accelerator, or with a sulfur vulcanization agent in the presence of an accelerator. For the purposes of this invention, sulfur vulcanizing agent means elemental sulfur (free sulfur) or sulfur donating vulcanizing agents, for example, an amine disulfide or a polymeric polysulfide. Preferably the sulfonamidesare used with both a sulfur vulcanization agent, preferably free sulfur, and an accelerator, preferably a primary accelerator. The invention is applicable to vulcanization accelerators of various classes using conventional accelerator levels. Regardless of what accelerator is used, the sulfonamides will still normally act as sulfur donors. For example, rubber mixes containing the aromatic thiazole accelerators which include N-cyclohexyl-Z-benzothiazolesulfenamide, 2-mercaptobenzothiazole, N- tertbutyl-2-benzothiazolesulfenamide, 2- benzothiazolyl diethyldithiocarbamate and 2- (morpholinothio)-benzothiazole can be used. Other thiazole accelerators which may be used include 2- (aminodithio)-thiazoles and 2-(aminotrithio)-thiazoles such as 2-(morpholinodithio)-benzothiazole. Amine salts of mercaptobenzothiazole accelerators, for example, the t-butylamine salt of mercaptobenzothiazole, and like salts of morpholine and 2,6-dimethylmorpholine can be used in the invention. Thiazole accelerators other than aromatic can be used. Stocks containing accelerators, for example, tetramethylthiuram disulfide, tetramethylthiuram monosulfide, aldehyde amine condensation products, thiocarbamylsulfenamides, thioureas, xanthates, and guanidine derivatives are substantially improved using the process of the present invention.

The sulfonamides of the invention can be used in natural and synthetic rubbers and mixtures thereof. Synthetic rubbers that can be improved by the process of this invention include homopolymers and copolymers of dienes, both conjugated and nonconjugated, e.g., 1,3-dienes such as 1,3-butadiene and isoprene. Examples of such synthetic rubbers include neoprene (polychloroprene), cis-'1,4 polybutadiene, cis-1,4 polyisoprene, butyl rubber, copolymers of 1,3-butadiene or isoprene with monomers such as styrene, acrylonitrile and methyl methacrylate. Ethylene/propylene terpolymers, for example ethylene/propylene/dicyclopentadiene terpolymers also benefit from the practice of the present invention.

The sulfonamides can be added to the rubbers by any conventional technique such as milling or Banburying.

All of the working examples herein are intended to illustrate but not limit the scope of the'present invention. Unless indicated otherwise, all partsare parts by weight.

The following examples, 1 to 7, illustrate the preparation of various sulfonamides of the present invention, and are not intended to limit the scope of the present invention.

EXAMPLE 1 To prepare N-( morpholinothio )-N-methyl-ptoluenesulfonamide, 4.72 grams (0.035 mole) of sulfuryl chloride was added to a refluxing solution of 15.1 grams (0.035 mole) N,N'-dimethyl-N,N'-dithiobis-(ptoluenesulfonamide) in ,60 ml. of methylene chloride. After 2 hours, the solution was cooled ina dry ice- .grams acetone bath and 12.2 grams (0.14 mole) of morpholine was added dropwise at 25 C. to 30 C. The precipitated morpholine hydrochloride was filtered off, the filtrate extracted with 100 ml. of water, dried (MgSO concentrated in vacuo, and the solid residue recrystallized from methanol to afford 17.3 grams (81.9%) of product with a melting point of 9092 C. Analysis of this product shows 20.7 percent sulfur and 9.29 percent nitrogen. Calculated percentages for C H N O S are 21.1 percent sulfur and 9.27 percent nitrogen. The infrared spectrum was consistent with the proposed structure.

EXAMPLE 2 N-( piperidinothio )-N-methyl-p-toluenesulfonamide was prepared as described in Example 1 except that 1 1.9 grams of piperidine were used in place of morpholine. The yield of product after recrystallization from methanol was 1 1.6 grams (55.2%) with a melting point of 65-67 C. Analysis of this product shows 9.29 percent nitrogen and 21.1 percent sulfur. Calculated percentages for C H N O S are 9.33 percent nitrogen and 21.3 percent sulfur.

EXAMPLE 3 EXAMPLE 4 To prepare N-methyl-N-(diisopropylaminothio)-ptoluenesulfonamide,0.25 mole of chlorine gas was added over a one-half hour period to a solution of 66.0

grams (0.25 mole) N,N.-.dithiobis(diisopropylamine) in 100 ml. of carbon tetrachloride at 5 C. The resulting diisopropylaminesulfenyl chloride solution was then added during one-half hour to a suspension of 0.50 mole of the sodium salt of N-methyl-ptoluenesulfonamidc in 500 ml. of toluene, maintaining the temperature of 0-l0 C. The reaction mixture was stirred for 1 hour after addition of the sulfenyl chloride, then filtered, and the filtrate concentrated in vacuo.

The resulting oily solid residuewas slurried in hexane, filtered, and the solid recrystallized from methanol to afford 79.1 grams (50.1%) product with a melting point of 8588 C. Analysis of the product shows 8.82 percent nitrogen and 19.1 percent sulfur. Calculated percentages for C H N O S are 8.86 percent nitrogen and 20.2 percent sulfur.

EXAMPLE 5 To prepare N-methyl-N-( 3methylpiperidinothio)-ptoluenesulfonamide, 0.15 mole of chlorine gas was added over a twenty minute period to a solution of 39.0

(0.15 mole) of N,N'-dithiobis-(3- methylpiperidine) in 250 ml. of toluene at 05 C. The resulting 3-methylpiperi'dinesulfenyl' chloride solution was then added during 45 minutes to asuspension of 0.30 mole of sodium. salt of EXAMPLE 6 To prepare N,N,N-trimethyl-N-(morpholinothio) sulfamide, 0.1 1 mole of chlorine gas was added over a 10 minute period toa mixture of 23.6 grams (0.10 mole) 4,4-dithiobis-(morpholine) in 100 ml. of 11011.1 ene at 05 C. The resulting morpholinesulfenyl chloride solution was then added dropwise to a suspension of 0.20 mole of the sodium salt of N,N,N-trimethylsulfamide in 250 ml. of toluene. After addition of the sulfenyl chloride, the mixture was stirred 1 hour, poured into 200 ml. of water, the upper toluene layer separated, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The resulting solid residue was recrystallized from methanol. The yield of product was 45.0 grams (88.3%) with a melting point of 57-60 C. Analysis showed 16.54 percent nitrogen and 24.96 percent sulfur. The calculated percentages C l-l N O S are 16.47 percent nitrogen and 25.10 percent sulfur.

EXAMPLE 7 N-( morpholinothio)-propanesultam was prepared by adding 0.099 mole of morpholinesulfenyl chloride in 50 ml. of toluene, dropwise to a suspension of 0.099 mole of the sodium salt of propanesultam in 150 ml. of toluene. The product was isolated by pouring the reaction mixture into 200 ml. of water, adding sufficient chloroform to dissolve the resultant solid, the organic layer separated, dried over anhydrous magnesium sulfate, and concentrated in vacuo. The resulting solid residue was recrystallized from 2-propanol-benzene. The yield of product was 18.5 grams (79.0%) with a melting point of l39142 C. Analysis shows 1 1.77 percent nitrogen and 26.94 percent sulfur. The calculated percentages for C-,H N 0 5 are l 1.76 percent nitrogen and 26.89 percent sulfur. v

The other compounds included within the practice of the present invention can be prepared by using the same or similar techniques as described in the preceding working examples. Synthetic routes to these compounds are not limited, however, to these particular reactions and procedures.

Tables 1, 11, Ill and 1V illustrate the use of various sulfonamides of the present invention with different rubber stocks. The compositions are intended only to be illustrative of the practice of the present invention and not limiting. Mooney Scorch tests were performed I using the large rotor as described in ASTM D 1646-61.

toluenesulfonamide in 300ml. of toluene. The reaction 5 A recorder was employed to continuously plot viscosity versus time. The number of minutes (IAS) required for the viscosity curve to rise five points above the minimum was taken as a measure of scorch inhibition. Larger values for (tAS) indicate a greaterresistance to scorch or premature vulcanization. 1

for

1 1 Data on vulcanizing characteristics were obtained with a Monsanto Oscillating Disc Rheometer, as described by Decker, Wise, and Guerry in Rubber World, page 68, December 1962. Pertinent data from this instrument are: t the minutes required for the Rheometer torque curve to rise four units above the minimum torque value, and the minutes required for the torque curve to reach 90 percent of the difference between the maximumand minimum torque values.

The t value is considered to be the time required to reach the optimum vulcanized state. The difference, (t I is indicative of the time necessary for actual vulcanization to take place after the scorch delay period has ended, i.e., is a relative measure of vulcanization rate. Compounds which increase t but do not greatly increase (I90 are preferred since these impart processing safety, yet do not require greatly extended vulcanization times.

ARh is the difference between the maximum and minimum torque obtained on the rheometer curve. It is used as a measure of the degree (state) of vulcanization.

The following Examples 8 to 45 illustrate the use of the sulfur donors of the present invention in both natural rubber and SBR (butadiene/styrene elastomer). Stock A was used in Examples 8 to 27 while Stock B was used in Examples 28 to 45. Both stocks were run with no sulfonamide (control), 0.5 part and 1.0 part of the sulfonamide.

The results obtained using Stock A are listed in Table 111 and the results using Stock B in Table IV. The rheometer data was obtained at a temperature of 275 F. in natural rubber and 302 F. in SBR. The Mooney Scorch data was determined at 250 F. in natural rubber and 270 F. in SBR.

The effect of the sulfonamides was measured by comparison with the control, i.e., the stock with no sulfonamide present. Ratios of the measurements for the sulfonamide compounded stocks over the measurements for the control stock are listed in the tables. The subscript indicates that the measurement was made on the control stock. Values of ARh/ARh,. which are over 1 .00 indicate that the sulfonamide has increased the state of vulcanization. Values of (1 t.,)/(t 1 which are less than 1.0, indicate an activating effect of the sulfonamide on the vulcanization rate. Values of [A /1A which are over 1.0 indicate that the sulfonamide has increased the scorch delay time, i.e., increased scorch resistance.

Table 11 contains a list of the various sulfonamides evaluated.

Table 11 sulfonamide A N-methyl-N-(morpholinothio)-p toluenesulfonamide B N-methyl-N-( piperidinothio )-p-toluenesu1fonamide C 4,4 -Trimethy1enedi-( piperidinothio )-bis-( N-methyl-ptoluenesulfonamide D N-methyl-N( 2,6-dimethylmorpholinothio )-p-toluenesulfonamide E N-methy1-N-(diisopropylaminothioJ-pdoluenesulfonamide F N ,N '-bis-( N-methyl-p-toluenesulfonamidothio )-piperazine G N-methyl-N-( tert-butylarninothio )-p-toluenesulfonamide H N-methy1-N-(dicyclohexylaminothio)-p-to1uenesu1fonamide I N-methyl-N-( N -a-cyanoefliylcyclohexylaminothio )-ptoluenesulfonamide .1 N-methy1-N-[ N ,N'-bis-(a-cyanoethyl )aminothio1-ptoluenesulfonamide K N-methy1-N-(morpholinothio)-p-chlorobenzenesulfonamide L N-methy1-N-(morpholinothio)-methanesu1fonamide M N-methy1-N-(N-a-cyanoethy1-tert-butylaminothi0)-p toluenesulfonamide N N-methy1-N-( 3-methy1piperidinothio )-p-toluenesulfonamide O N,N,N '-trimethyl-N morpho1inothio)-su1famide P N,N-dimethy1-N -p-to1y1-N morpholinothio )-sulfamide Q N-( morpholinothio )-propanesu1tam R N-phcny1-N-(morpholinothio)-benzenesulfonamide S N,N'-bis( morpholinothio)-N,N '-ethylenebis( Nmethyl-ptoluenesulfonamide) T N-methy1-N-(aminothio)-p-to1uenesulfonamide Table 111 Natural Rubber en 4) ARh/ARh. (t -t. tA5/tA5,. (parts) (parts) (parts) Sulfo- I Exp. namide 0.5 1.0 0.5 1.0 0.5 1.0

8 A 1.13 1.24 .95 1.00 1.28 1.46 9 B 1.25 1.28 .80 .85 1.08 1.40 10 C 1.15 1.19 .91 199 1.01 1.18 11 D 1.14 1.22 .94 .94 1.29 1.42 12 E 1.14 1.23 .94 .90 1.21 1.25 13 F 1.05 1.14 1.07 1.11 1.18 1.16 14 G 1.16 1.24 .86 .96 .97 .88 15 H 1.20 1.19 .80 .84 1.05 1.26 16 1 1.11 1.13 .99 1.02 1.18 1.44 17 J 1.07 1.12 .94 .91 .95 .95 18 K 1.17 1.18 .83 .87 1.20 1.45 19 L 1.23 1.23 .83 .89 1.20 1.69 20 M 1.09 1.09' .99 1.06 1.18 1.37 21 N 1.24 1.32 .81 .84 1.23 1.43 22 O 1.14 1.23 .93 .98 1.23 1.45 23 P 1.16 1.25 .86 .88 1.23 1.41 24 Q 1.20 1.28 .96 .98 1.38 1.57 25 R 1.12 1.12 .88 .83 .97 1.07 26 S 1.12 1.24 1.04 1.00 1.30 1.27 27 T 1.08 1.12 .88 .80 .78 .60

As indicated by the above data in Table 111, the sulfur donors increased the state of vulcanization in every instance. In addition, all compounds acted as activators and/or retarders. Over half of the compounds not only increased the state of vulcanization and improved resistance to scorching, but also increased the rate of vulcanization.

Table lV-Continued I R (rm-m 1 ARh/ARh," r I (u -t 1 tA5/tA5,.

(p r (par (p Sulfo- Exp namide 0.5 1.0 0.5 1.0 0.5 1.0

33 F 1.06 1.10 .86 .82 1.42 1.52 34 O 1.08 1.15 578 .71 .98 .95 35 H 1.05 1.09 .55 .50 1.07 1.11 36 l 1.00 1.04 1.00 .96 1.15 1.12 37 .1 1.12 1.09 1.01 .94 38 K 1.09 1.17 .81 .76 1.08 1.16 39 L 1.23 1.40 .78 .73 .81 .97 40 M 1.07 1.14 .97 .95 1.15 1.16 41 O 1.08 1.19 .73 .63 1.07 1.25 42 P 1.06 1.12 .74 .61 1.07 1.17 43 Q 1.11 1.18 .70 .57 1.20 1.11 44 R 1.06 1.00 .87 .73 1.07 .89 45 S 1.08 1.12 .77 .62 1.11 1.23

' The Mooney Scorch data for the control was abnormally low. Therefore the ratios have been omitted. Sulfonamide 1. however, did act as a retarder as indicated by the Monsanto Rhcometcr t values. The control had a value of 12.6 while sulfonamide J had a value of 13.9 at the 0.5 part level and 13.8 at the 1.0 part level.

As indicated by the above-data in Table IV, only five of the compounds failed to act as retarders in SBR at both the 0.5 and 1.0 part level. Only two failed to act as activators. All of the compounds acted as sulfur donors to increase the state of vulcanization with two exceptions; 1 did not act as a sulfur donor at the 0.5 part level, and R did not act as a sulfur donor at the 1.00 part level. However, both acted as activators.

The sulfur donors can be used with any'accelerator. N-methyl-N-(morpholinothio)-p-toluenesulfonamide was used at the 0.5 part level with 2-(morpho1inothio)- benzothiazole (0.5 part) and sulfur innatural rubber. The sulfonamide notonly increased the state of vulcanization but also acted as a retarder, while having little adverse effect on the vulcanization rate.

When used at the 1.0 part level in a butadiene/styrene elastomer with sulfur and 1.0 part of N- eyclohexyl-2-benzothiazolesulfenamide, the same sulfonamide not only acted as a sulfur donor and a retarder, but acted as an activator as well.

N-methyl-N-(morpholinothio)-p-toluenesulfonamide was used in a carbon black loaded natural rubber system using 2-(morpholinodithio)-benzothiazole as a primary accelerator and free sulfur. In one instance 0.25 part of diphenylguanidine was used and in another instance, 020 part of tetramethylthiuram disulfide. In both instances the state of vulcanization and scorch delay time were increased although the rate of vulcanization was decreased.

N-methyl-N-( morpholinothio )-p-toluenesulfonamide was used in a carbon black loaded natural rubber system, in one instance with 2-(morpholinothio benzothiazole and in another instance with mercaptobenzothiazole, using 2.5 parts of free sulfur. The sulfonamide increased the state of vulcanization, the rate of vulcanization and the scorch delay time in both instances.

The above examples are not intended to be limiting but rather illustrative. Any of the sulfur donors, accelerators and rubbers described earlier herein can be substituted in the preceding examples. In addition, the levels of the sulfur donors and other components in said examples could be altered in accordance with the general teachings herein.

The additives of this invention can be used at various concentrations as low as 0.25 part per 100 parts by weight of rubber and even as low as 0.10 or even 0.05 part. Conventional levels would frequently be 0.5 and 1.0 part, although levels as high as 1.5, 3.0, 5.0 and even 10 parts can be used. Most frequently the concentration ranges from 0.25 to 5.0 parts, more preferably from 0.25 to 3.0 parts and most preferably from 0.25 to 1.50 parts.

The sulfur donor compounds of the present invention are preferably added to the rubbery polymer at the same time that the accelerator is added, although this order of addition is not necessary to the successful utilization of the compounds of this invention.

The compounds of the present invention are effective inithe presence of organic accelerators whether they are diarylguanidines such as diphenylguanidine, or thiazoles more specifically benzothiazyl amino disulfides, such as 2-(morpholinodithio)-benzothiazole, or thiazoles (also sulfenamides), more specifically thiazolesulfenamides, and even more specifically benzothiazolesulfenamides such as 2-(morpholinothio') benzothiazole and N-cyc1ohexyl-2-benzothiazolesulfenamide, i.e., regardless of what type of organic,accelerator is used. Thiuram sulfides such as tetramethylth-iuram monosulfide and disulfide and tetraethylthiu'ram monosulfide and disulfide may also be used as well as other benzothiazolesulfenamides such'as N-(t-butyl )'-2- benzothiazolesulfenamide.

Various organic accelerators useful within 't tice of this invention are describedand illustrated i'n the Vanderbilt Rubber Handbook, 1 968 Edition, RI: derbilt Company, Inc., particularly. dt'pages 242" and 244 and also in the bulletin of the Elastomer, Chemicals Dept. of the E. l. Du Pont de Nemours and Co."(inc.) entitled, Accelerators, vulcanizing Agents and Retarders, Brochure No. SD AS4457.

The polymers in which the sulfonamides of the present invention are incorporated remain suitable for their art recognized uses, e.g., in tires and industrial products.

Compounds referred to earlier herein as being retarders and/or activators in natural rubber and SBR are merely illustrative and not limiting.

The balanced processing and vulcanization characteristics are most often obtained when free sulfur (elemental sulfur) and a primary accelerator are used with the sulfonamide.

Sometimes compounds are both a sulfur donor (and therefore a sulfur vulcanizing agent) and an accelerator, e.g., 2-(morpholinodithio)-benzothiazole. Such compounds can be used with the sulfonamides, with or without another sulfur vulcanizing agent and/or another accelerator.

The compounds of the present invention can be used effectively in any sulfur vulcanizable polymer and with any organic accelerating agent.

While certain representative embodiments and details have been shown for the purpose of illustrating the invention, it will be apparent to those skilled in this art that various changes and modifications may be made therein without departing from the spirit or scope of the invention.

What is claimed is:

1. A sulfur vulcanizable diene polymer having incorporated therein a sulfonamide having the followng structural formula wherein R is selected from the group consisting of alkyl radicals having 1 to 20 carbon atoms, cycloalkyl radicals having to 20 carbon atoms, aralkyl radicals having 7 to 20 carbon atoms, aryl radicals having 6 to 20 carbon atoms and wherein R can also be the radical wherein R and R are selected from the group consisting of alkyl radicals having 1 to 20 carbon atoms, cycloalkyl radicals having 5 to 20 carbon atoms, aralkyl radicals having 7 to 20 carbon atoms, and aryl radicals having 6 to 20 carbon atoms and wherein R and R can be joined through a member of the group consisting of .CH O, and -S to constitute with the attached nitrogen atom a heterocyclic ring, and wherein R and R -are selected from the group consisting of hydrogen, cyanoalkyl radicals having 3 to 21 carbon atomsandradicals, other than aryl, described for R and Rf and. can join to form the heterocyclic ring described for Rland R and wherein R is selected from the group'consisting of alkylene radicals having 1 to 10 carbon atoms, cycloalkylene radicals having 6 to carbon atoms and arylene radicals having 6 to 20 carbon atoms.

2. The sulfur vulcanizable diene polymer according to claim 1 wherein the polymer has incorporated therein an organic accelerating agent.

3. The sulfur vulcanizable diene polymer according 16 to claim 1 wherein the polymer has incorporated therein a sulfur vulcanizing agent. g g

4. The sulfur vulcanizable diene polymer according to claim 2 wherein the organic accelerating agent is a primary accelerator and the polymer has incorporated therein elemental sulfur. I

5. The sulfur vulcanizable diene polymer according to claim 1 wherein the sulfonamide is present-in the amount of from 0.25 part to 5.0 parts by weight per parts by weight of polymer.

6. The sulfur vulcanizable diene polymer according to claim 1 wherein R is selected from the group consisting of methyl, ethyl, 2-propyl, n-butyl, n-propyl, phenyi, p-tolyl, p-chlorophenyl, dimethylamino, morpholino, piperidino, p-methoxyphenyl, p-nitrophenyl and cyclohexyl, wherein N-B-cyanoethyl-ntylamino and wherein R is selected from the group 1,4-.

consisting of ethylene, 1,3-propylene, cyclohexylene and p-phenylene.

7. The sulfur vulcanizable diene polymer according to claim 1 wherein the sulfonamide is N,N- bis(morpholinothio )N,N -ethylenebis-( N-methyl-p- N-B-cyanoethylcyclohexylamino,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. 1 5,898,206

DATED I August 5' INVENTOR(S) Roger J. Hopper and John P. Lawrence It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 15, "N-methyl-N-(morpholinothio)methanosulfonamide" should read N-methyl-N-(morpholinothio)- methanesulfonamide Column 6, line 39, "hexahydropyridimine" should read hexahydropyrimidine Column 12, Table II, in the sulfonamides I, J and M, the "or" should be [5 Signed and Scaled this twen ty-ez'ght D 3} Of October 1 975 [SEAL] A ttest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner nfParents and Trademarks 

1. SULFUR VULCANIZABLE DIENE POLYMER HAVING INCORPORATED THEREIN A SULFONAMIDE HAVING THE FOLLOWING STRUCTURAL FORMULA
 2. The sulfur vulcanizable diene polymer according to claim 1 wherein the polymer has incorporated therein an organic accelerating agent.
 3. The sulfur vulcanizable diene polymer according to claim 1 wherein the polymer has incorporated therein a sulfur vulcanizing agent.
 4. The sulfur vulcanizable diene polymer according to claim 2 wherein the organic accelerating agent is a primary accelerator and the polymer has incorporated therein elemental sulfur.
 5. The sulfur vulcanizable diene polymer according to claim 1 wherein the sulfonamide is present in the amount of from 0.25 part to 5.0 parts by weight per 100 parts by weight of polymer.
 6. The sulfur vulcanizable diene polymer according to claim 1 wherein R is selected from the group consisting of methyl, ethyl, 2-propyl, n-butyl, n-propyl, phenyl, p-tolyl, p-chlorophenyl, dimethylamino, morpholino, piperidino, p-methoxyphenyl, p-nitrophenyl and cyclohexyl, wherein
 7. The sulfur vulcanizable diene polymer according to claim 1 wherein the sulfonamide is N,N''-bis(morpholinothio)N,N''-ethylenebis-(N-methyl-p-toluenesulfonamide). 